CN102218334B - Antimonial ammoxidation catalyst - Google Patents

Antimonial ammoxidation catalyst Download PDF

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CN102218334B
CN102218334B CN2010101478099A CN201010147809A CN102218334B CN 102218334 B CN102218334 B CN 102218334B CN 2010101478099 A CN2010101478099 A CN 2010101478099A CN 201010147809 A CN201010147809 A CN 201010147809A CN 102218334 B CN102218334 B CN 102218334B
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catalyst
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ammoxidation catalyst
antimonial
isophthalodinitrile
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CN102218334A (en
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顾龙勤
陈亮
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to an antimonial ammoxidation catalyst which mainly solves the problem that in the prior art the catalyst is difficult to adapt for the requirement of a fluidized bed and requires raw materials with higher price and the target outcome m-phthalonitrile has low yield. The antimonial ammoxidation catalyst comprises a catalyst active component which is a combination with the following chemical formula by atomic ratio: V1.0SbaAbBcCdOx, wherein A is at least one type of metal out of lithium, sodium, kalium or rubidium or cesium; B is at least one type of metal out of magnesium, calcium, barium, chrome, tungsten, molybdenum, manganese, iron, cobalt, nickel or tin; and C is at least one type of metal out of boron or phosphor. The technical scheme better solves the problem and can be used for industrial production.

Description

The ammoxidation catalyst that contains antimony
Technical field
The present invention relates to a kind of catalyst that contains the standby isophthalodinitrile of prepared by ammoxidation of antimony.
Background technology
Isophthalodinitrile (being called for short IPN) is the important Organic Ingredients of organic synthesis, and it is efficient, low toxicity antimildew disinfectant through the synthetic termil (Bravo) of chlorination; The m-xylene diamine (MXDA) that gets through Hydrogenation is the epoxy curing agent of superior performance, also is the raw material of polyurethane resin and nylon resin.
Simple, the most most economical manufacture method of isophthalodinitrile is to obtain with meta-xylene gas phase ammonoxidation reaction under catalyst action, and its core technology is catalyst.
The fifties Japan is clear to have developed the synthetic isophthalodinitrile production technology of ammoxidation of m-xylene fixed bed with the electrician, the seventies Mitsubishi gas company and U.S. Badger company have developed fine grained fluidisation bed isophthalodinitrile commercial plant cooperatively, mainly for the production of m-benzene diisocyanate, the level of production of isophthalodinitrile is improved.In recent years, along with the expansion in termil (Bravo) and m-xylene diamine (MXDA) market, the production scale of the isophthalodinitrile of China (IPN) is the gesture of rapid growth, and its catalyst and production technology research thereof are also unprecedented popular.
In the employed catalyst of ammoxidation of m-xylene reaction technology, the V series catalysts is the most general and effective a kind of catalyst system and catalyzing, generally all uses in early days simple vanadium component or vanadium component to add a small amount of cocatalytic element, and its activity is too high, selectively relatively poor, yield is lower.Form four kinds of compositions such as mainly containing V-Cr, V-Mo, V-P and Sb-Fe from recent catalyst, because Sb series catalysts preparation and reaction condition etc. are relatively more complicated, the economy of ammoxidation of aromatic hydrocarbon technology that makes this catalyst relatively poor and do not promote commercial Application always.Opposite V-Cr catalyst preparation is simple, good reproducibility, ammoxidation of aromatic hydrocarbon is had higher reactivity, but the catalyst activity of two components is still too high, easily causes deep oxidation, can generate a large amount of CO 2, CO, HCN.And this catalyst has stronger oxidative decomposition capacity to ammonia, has greatly increased the consumption of ammonia.
The eighties Mitsubishi gas company has released four component catalysts such as V-Cr-B-Mo, V-Cr-B-P, and catalytic perfomance increases on the basis of former three components, but it reacts by-product especially CO, CO 2Growing amount is still higher.The nineties Mitsubishi gas has been announced again (EP0525367A 1) catalyst that forms of V-Cr-B-P-Mo five, improved the growing amount of reaction by-product, improved the yield of isophthalodinitrile, but the document points out to use the catalyst raw material of expensive ammonium phosphomolybdate, just can obtain desirable reaction result.
Add K, Fe and W in the VSb/Al of BASF preparation or the Si catalyst, be prepared into fixed bde catalyst, its isophthalodinitrile yield is 78.8%, but according to disclosed preparation method, can't make fluid catalyst.The fluid catalyst (99113575.X) of Shanghai Petroleum Chemical Engineering Institute research and development is V-Cr system, and it does not contain Sb, and the yield of isophthalodinitrile also only is 78.8%.
The isophthalodinitrile method for preparing catalyst is also varied, and domestic Wuhan University once made with infusion process and coarse granule spherical silica gel.The isophthalodinitrile yield is lower in industrial production, and catalyst life is also shorter, approximately just must change in six months, otherwise its product yield declines to a great extent.Chengdu Univ. of Science ﹠ Technology is once with dipping preparation ammoxidation of m-xylene catalyst again after the carrier reaming, has the problems referred to above equally and fails to realize commercial Application.
Summary of the invention
Technical problem to be solved by this invention is that in the past catalyst is difficult to adapt to the fluid bed requirement, needs to use the more expensive raw material of price, and the not high problem of target product isophthalodinitrile yield provides a kind of new fluid catalyst for the preparation of isophthalodinitrile.This catalyst have the raw material of use inexpensive, be easy to get, and have the characteristics of good reactivity and higher isophthalodinitrile yield.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ammoxidation catalyst that contains antimony, take silica as carrier with the following composition of atomic ratio measuring chemical formula:
V 1.0Sb aA bB cC dO x
A is selected from least a in lithium, sodium, potassium, rubidium or the caesium in the formula;
B is selected from least a in magnesium, calcium, molybdenum, barium, chromium, tungsten, manganese, iron, cobalt, nickel or the tin;
C is selected from least a in boron or the phosphorus;
Wherein the span of a is 0.3～2.0;
The span of b is 0.01～0.5;
The span of c is 0.05～1.0;
The span of d is 0～2.0;
X is the summation that satisfies other element valence requisite oxygen atomicity;
The content of carrier silica is 30～90% by weight percentage in the catalyst.
In the technique scheme, the preferable range of A is to be selected from least a in lithium, potassium, caesium or the sodium; The B preferable range is selected from least a in chromium, iron, manganese, tungsten, molybdenum, cobalt or the nickel.The preferred span of a is 0.8～1.5; The preferred span of b is 0.05～0.2; The preferred span of c is 0.1～0.5; The preferred span of d is 0.3～1.0.In the catalyst content of carrier silica by weight percentage preferable range be 45～65%.
Catalyst component of the present invention also is applicable to be prepared into fixed bde catalyst except being prepared into fluid catalyst, and all has good catalytic activity.
V 2O 5, Sb 2O 3And the corresponding oxide of each element of general formula A, B, C is the initiation material of catalyst, also can select other compound to make raw material.Example:
Vanadium raw materials: ammonium metavanadate, vanadic sulfate, organic acid vanadium such as vanadium oxalate or tartaric acid vanadium;
Antimony raw material: antimony trioxide, metaantimmonic acid, stibate (ammonium), nitric acid antimony or antimony organic: antimony acetate, antimony oxalate ammonium, potassium antimony tartrate, sodium antimony tartrate or antimony tartrate;
A raw material: nitrate, element oxide or corresponding alkali;
B raw material: nitrate;
C raw material: the sour ammonium of acid or solubility;
Silicon raw material: use Ludox, silicon gel or silica as the carrier of catalyst.
The preparation of catalyst makes by specific method: A, B, the C solution of solubility are added to V 2O 5, Sb 2O 3Oxalic acid solution in, get suspension material mixture slurry, add solvent then spent glycol, oxalic acid etc. such as needs.The fluid catalyst slurry after spraying shaping drying, roasting.The fixed bde catalyst slurry is dry, roasting after evaporation.
The roasting of catalyst of the present invention can be divided into decomposition and two stages of high-temperature roasting of each element salt in the catalyst.The decomposition temperature of salt is 100～200 ℃, and preferable range is 150～180 ℃, and the time is 2～20 hours, and preferable range is 3～15 hours; Sintering temperature is 450～800 ℃, and preferable range is 450～650 ℃, and the time is 2～15 hours, and preferable range is 5～10 hours.Decomposition and high-temperature roasting can be carried out in two roasters, also can carry out in a roaster, or will decompose in the continous way rotary roasting furnace with high-temperature roasting and carry out simultaneously.
Oxide content is with V in the catalyst 2O 5, Sb 2O 3, acidic oxide, basic anhydride and the above metal of divalence the weight percent meter of highest price oxide.
Raw material alkylbenzene of the present invention can be: toluene, meta-xylene, paraxylene, mesitylene etc.
The present invention is in when reaction during take air as oxygen source, and the mixture concentration of alkylbenzene is 0.1～10% (volume), preferable range 0.2～5.0% (volume).
The use amount of the present invention's ammonia when reaction is the several times of theoretical amount at least, and a high proportion of ammonia is favourable to reaction, but has recovery and the pollution problem of ammonia.The ammonia amount of this technique is 2～13 times of theoretical amount, and preferable range is 3～10 times.
Amount of oxygen of the present invention is 1.5 times of theoretical amount at least, and more suitable scope is 2～10 times.Usually make oxygen source with air, nitrogen, carbon dioxide, water vapour can be used as inert diluent.
Technological reaction temperature of the present invention is 300～500 ℃, and preferable range is 330～480 ℃; When temperature was lower than 300 ℃, reaction conversion ratio was low, and deep oxidation reacts serious when being higher than 500 ℃, by-product CO 2, CO, HCN content obviously increase, fragrant nitrile yield descends.The optimum temperature of this reaction depends on the number, position, the concentration of starting material, the Active components of catalyst, the factors such as roasting condition, reaction contact time and load of catalyst of aromatic hydrocarbons alkyl.
Larger mobility scale is arranged time of contact of the present invention, and generally at 0.2～20 second, preferred scope is 0.5～15 second.
The present invention reacts under normal pressure usually, also can depress reaction adding.
Catalyst of the present invention both can be used for fixed bed, can be used for again moving bed and fluid bed.
The conversion ratio of meta-xylene among the embodiment of catalyst of the present invention, isophthalodinitrile is selective and the m-dicyanobenzene once through yield is defined as follows:
The catalyst of the embodiment of the invention investigate be
Figure GSA00000086578800044
Carry out in the stainless steel fluidized-bed reactor, addition 550 grams of catalyst, reacting system pressure is 0.01MPa.
Owing to using antimony element, greatly reduce the decomposition of ammonia among the present invention, in reaction, reduced the ammonia ratio, so both reduced the unit consumption of ammonia, reduced again three wastes processing cost.Owing to making fine grain fluid catalyst, solved reactor engineering enlarge-effect on the other hand.In V, Sb catalyst, add suitable category-A basic anhydride and C class acidic oxide and the above metallic element oxide of category-B divalence, greatly improved physics, the chemical property of catalyst, reduced by-product CO 2, CO and HCN growing amount, improved the reaction yield of isophthalodinitrile.Add in addition after the alkali metal, greatly strengthened the abrasion strength resistance of catalyst, improved reaction selectivity.Catalyst of the present invention is 425 ℃ of reaction temperatures, and under the reaction pressure 0.01MPa condition, examination isophthalodinitrile yield is the highest in fluid bed still can reach 80.8%, has obtained preferably technique effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
The catalyst preparation:
201 gram V 2O 5Be added to the temperature that is comprised of 440 ml waters 420 gram oxalic acid and be in 80～90 ℃ the solution, fully vanadium oxalate solution is reacted to get in stirring.
With 40% (weight) SiO 2Ludox 1250 gram under agitation slowly be added in the mentioned solution, then add respectively by 505 gram antimony oxalate ammonium [2 (NH 4) 3Sb (C 2O 4) 32H 2O] and 300 the ml waters solution, the 68.6 gram H that form 3BO 3The solution and 117.6 that forms with 560 ml waters restrains (NH 4) 6Mo 7O 244H 2The solution that O and 50 ml waters form, 0.11 mole of phosphoric acid solution adds 9.4 gram Na NO at last 3Solution with 20 ml waters form mixes, and heating evaporation to solid content is 42% (weight), gets viscous paste.
The spraying of above-mentioned slurry is shaped, 250 ℃ of sprayer gas feed temperature, and 130 ℃ of outlet temperatures, the catalyst after the shaping, gets catalyst and forms: V 550 ℃ of roastings 8 hours in 130 ℃ of dryings 12 hours 1Sb 1B 0.5P 0.05Mo 0.3Na 0.05/ SiO 2Catalyst master loading capacity ratio is 50/50, and the average grain diameter of catalyst is 200 orders.
The performance evaluation of catalyst:
Processing compound (mole): meta-xylene: ammonia: air=1: 8: 41,60 grams per liters hour of loading
Reaction temperature: 425 ℃.
Result: meta-xylene conversion ratio 98.5%
Between two benzonitriles selective 82.0%
Between two benzonitrile yields 80.8%
[embodiment 2～14]
Method for preparing catalyst changes composition or the proportioning of catalyst with embodiment 1, presses evaluating catalyst condition among the embodiment 1, and evaluation result is listed in the table below 1.
Table 1
Embodiment Catalyst The meta-xylene conversion ratio, % Isophthalodinitrile is selective, % The isophthalodinitrile yield, %
2 V 1.0Sb 1.0B 0.5P 0.5Co 0.3Na 0.05/SiO 2 97.0 80.2 77.8
3 V 1.0Sb 1.0B 0.7P 0.5Ni 0.3Na 0.0/SiO 2 95.8 80.2 76.8
4 V 1.0Sb 1.0B 0.5Mo 0.3Na 0.05/SiO 2 97.4 76.6 74.6
5 V 1.0Sb 1.0P 0.5Co 0.3Na 0.05/SiO 2 97.8 73.9 72.3
6 V 1.0Sb 1.0B 0.5P 0.05Mo 0.3K 0.3Na 0.05/SiO 2 96.4 78.1 75.3
7 V 1.0Sb 0.8B 0.5P 0.05Mo 0.3Na 0.05/SiO 2 98.5 77.9 76.7
8 V 1.0Sb 0.9B 0.5P 0.05Mo 0.3Na 0.05/SiO 2 98.0 78.8 77.2
9 V 1.0Sb 1.0B 0.5P 0.07Mo 0.3K 0.05Cs 0.015/SiO 2 97.0 77.8 75.5
10 V 1.0Sb 1.0B 0.5P 0.5W 0.1K 0.03Cs 0.02/SiO 2 95.7 76.7 73.4
11 V 1.0Sb 1.0B 0.5P 0.2K 0.05Cr 0.3Cs 0.025/SiO 2 96.8 79.5 77.0
12 V 1.0Sb 1.0B 0.5P 0.3Fe 0.3Na 0.05/SiO 2 97.3 74.5 72.5
13 V 1.0Sb 1.0B 0.5P 0.2W 0.3Na 0.06/SiO 2 96.0 76.5 73.4
14 V 1.0Sb 1.0B 0.5P 0.2Cu 0.3Na 0.06/SiO 2 96.5 80.1 77.3

Claims (4)

1. ammoxidation catalyst that contains antimony, take silica as carrier with the following composition of atomic ratio measuring chemical formula:
V 1.0Sb aA bB cC dO x
A is selected from least a in sodium, potassium, rubidium or the caesium in the formula;
B is selected from least a in calcium, barium, cobalt or the nickel;
C is selected from least a in boron or the phosphorus;
Wherein the span of a is 0.3～2.0;
The span of b is 0.01～0.5;
The span of c is 0.05～1.0;
The span of d is greater than 0 to 2.0;
X is the summation that satisfies other element valence requisite oxygen atomicity;
The content of carrier silica is 30～90% by weight percentage in the catalyst.
2. the described ammoxidation catalyst that contains antimony according to claim 1 is characterized in that A is selected from least a in potassium, caesium or the sodium; B is selected from least a in cobalt or the nickel.
3. the described ammoxidation catalyst that contains antimony according to claim 1, the span that it is characterized in that a is 0.8～1.5; The span of b is 0.05～0.2; The span of c is 0.1～0.5; The span of d is 0.3～1.0.
4. the described ammoxidation catalyst that contains antimony according to claim 1, the content that it is characterized in that carrier silica in the catalyst is 45～65% by weight percentage.
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CN109876794B (en) * 2018-12-17 2022-02-18 中南民族大学 Special catalyst for preparing isophthalonitrile through ammoxidation reaction, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1100091A (en) * 1992-06-26 1995-03-15 标准石油公司 Method for ammoxidation of olefins
CN1426834A (en) * 2001-12-21 2003-07-02 沙地基本工业公司 Catalyst composition for ammoxidation of parafins and olefins, and preparing process and use thereof
CN101267883A (en) * 2005-07-20 2008-09-17 巴斯夫欧洲公司 Full catalyst, production thereof, and use thereof in an ammoxidation process

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US6916763B2 (en) * 2002-11-27 2005-07-12 Solutia Inc. Process for preparing a catalyst for the oxidation and ammoxidation of olefins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1100091A (en) * 1992-06-26 1995-03-15 标准石油公司 Method for ammoxidation of olefins
CN1426834A (en) * 2001-12-21 2003-07-02 沙地基本工业公司 Catalyst composition for ammoxidation of parafins and olefins, and preparing process and use thereof
CN101267883A (en) * 2005-07-20 2008-09-17 巴斯夫欧洲公司 Full catalyst, production thereof, and use thereof in an ammoxidation process

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